WO2020122472A2 - Matériau d'alliage de magnésium et son procédé de production - Google Patents

Matériau d'alliage de magnésium et son procédé de production Download PDF

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Publication number
WO2020122472A2
WO2020122472A2 PCT/KR2019/016489 KR2019016489W WO2020122472A2 WO 2020122472 A2 WO2020122472 A2 WO 2020122472A2 KR 2019016489 W KR2019016489 W KR 2019016489W WO 2020122472 A2 WO2020122472 A2 WO 2020122472A2
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Prior art keywords
weight
magnesium alloy
alloy material
molten metal
rare earth
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Ceased
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PCT/KR2019/016489
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English (en)
Korean (ko)
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WO2020122472A3 (fr
Inventor
박성수
백수민
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UNIST Academy Industry Research Corp
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UNIST Academy Industry Research Corp
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Priority to CN201980065305.1A priority Critical patent/CN112789360A/zh
Priority to DE112019006206.9T priority patent/DE112019006206T5/de
Priority to JP2021529823A priority patent/JP7323616B2/ja
Publication of WO2020122472A2 publication Critical patent/WO2020122472A2/fr
Publication of WO2020122472A3 publication Critical patent/WO2020122472A3/fr
Priority to US17/132,613 priority patent/US20210115538A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/04—Casting aluminium or magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent

Definitions

  • One embodiment of the present invention relates to a magnesium alloy material and its manufacturing method.
  • Magnesium alloy has the lowest specific gravity, excellent specific strength and non-rigidity among practical structural metal materials, and recently, demand for automobiles and electronic products requiring weight reduction is increasing.
  • demand for automobiles and electronic products requiring weight reduction is increasing.
  • medical biodegradable implants has been suggested, and currently, research on the development of magnesium materials for surgical fracture implants and vascular/digestive stents is actively underway.
  • magnesium alloys such as magnesium-aluminum, magnesium-zinc, and magnesium-tin, which are developed as magnesium alloys, not only have the characteristics of easily igniting at high temperatures, but also exhibit a very high corrosion rate compared to aluminum alloys that are competitive metals. have. This acts as a stumbling block inhibiting the commercialization of magnesium alloys as structural and medical materials.
  • the magnesium alloy material Al: 0.03 to 16.0% by weight, Mn: 0.015 to 1.0% by weight, Sc: 0.02 to 0.5% by weight, lanthanide rare earth elements (RE): 0.03 to 2.0% by weight, and residual Mg and unavoidable impurities, and the rare earth elements (RE) are La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb Or it provides a magnesium alloy material comprising a combination of these.
  • the rare earth element (RE) may include 0.1 to 1.0% by weight.
  • Zn may further include less than 5.0% by weight.
  • Zn 0.1 to 4.5% by weight may be further included.
  • Ca 2.0% by weight or less may be further included. More specifically, it may contain 0.5 to 2.0% by weight.
  • Y 0.5% by weight or less may be further included. More specifically, it may include more than 0 and 0.3% by weight or less.
  • Al 0.03 to 16.0 wt%, Mn: 0.015 to 1.0 wt%, Sc: 0.02 to 0.5 wt%, lanthanide rare earth element (RE): 0.03 to 100% by weight
  • a molten metal containing 2.0% by weight, residual Mg and unavoidable impurities
  • casting the molten metal to prepare a cast material; including, the rare earth elements (RE) La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, It provides a method for producing a magnesium alloy material containing Yb or a combination thereof.
  • the molten metal may include the rare earth element (RE) at 0.1 to 1.0% by weight.
  • RE rare earth element
  • Zn may further include less than 5.0% by weight.
  • Ca 2.0% by weight or less may be further included. More specifically, it may contain 0.5 to 2.0% by weight.
  • Y 0.5% by weight or less may be further included.
  • the cast material may further include rolling, extrusion, drawing, forging, or a combination thereof.
  • Casting the molten metal to prepare a cast material may be carried out in a temperature range of 600 °C to 800 °C.
  • the magnesium alloy may be variously used as a cast material, a rolled material, an extruded material, a drawing material, a forging material, and the like, which can be practically applied to industries requiring excellent corrosion resistance.
  • 1 is a scanning electron microscope photograph showing secondary phase particles formed inside a rolled Mg-3Al-0.3Mn-0.1Sc-1Zn alloy.
  • FIG. 2 is a scanning electron microscope photograph showing secondary phase particles formed inside a rolled alloy of Mg-3Al-0.3Mn-0.1Sc-1Zn-0.3Gd alloy.
  • Magnesium alloy material that is an embodiment of the present invention, Al: 0.03 to 16.0 wt%, Mn: 0.015 to 1.0 wt%, Sc: 0.02 to 0.5 wt%, rare earth element (RE): 0.03 to 2.0 wt%, based on 100 wt% %, a magnesium alloy material containing residual Mg and unavoidable impurities.
  • the rare earth element may include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or combinations thereof.
  • the reason for limiting the composition and composition of the magnesium alloy material is as follows.
  • aluminum contributes to an increase in the strength of the alloy through solid solution strengthening and precipitation strengthening, and improves corrosion resistance by improving the stability of the oxide film during corrosion. Accordingly, if the content of aluminum is too small, an effect of increasing strength and improving corrosion resistance may not be expected. On the other hand, if the content of aluminum is too large, the fraction of brittle particles containing aluminum may be excessive, causing a problem that the ductility of the alloy becomes weak.
  • Manganese contributes to an increase in the strength of the alloy by strengthening solid solution. In addition, by forming compound particles that absorb impurities in the alloy, it serves to improve the corrosion resistance of the magnesium alloy.
  • the magnesium alloy containing scandium may have an effect of improving the corrosion resistance of manganese.
  • the fraction of particles containing manganese is excessive, and thus microgalvanic corrosion is rather promoted, thereby reducing corrosion resistance. Accordingly, the upper limit of manganese may be limited as in one embodiment of the present invention.
  • it may include 0.015 to 1.0% by weight of Mn, based on 100% by weight of the magnesium alloy material. Specifically, it may be 0.015 to 0.6% by weight.
  • the corrosion rate is increased as described above, and the effect of improving corrosion resistance due to the addition of rare earth elements may be negligible.
  • Scandium plays a role in improving the corrosion resistance of the magnesium alloy material by participating in changes in the electrochemical properties of the secondary phase particles.
  • the fraction of secondary phase particles containing scandium may be small, and thus it may be difficult to expect an effect of adding scandium to improve corrosion resistance.
  • the fraction of particles containing scandium may be excessive, which may cause microgalvanic corrosion to be promoted and an increase in alloy material price.
  • the rare earth element can improve corrosion resistance by participating in changes in the electrochemical properties of secondary phase particles.
  • the rare earth element (RE) is a lanthanide rare earth element La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Combinations of these.
  • the rare earth elements when the above elements are added, the effect of improving corrosion resistance may be excellent.
  • the effect of improving corrosion resistance can be further expected by adding scandium and the lanthanide rare earth elements excluding scandium in the above-described content range.
  • the content of the rare earth element is too small, the effect of improving corrosion resistance may be negligible, and if too large, the cost of manufacturing the alloy may be excessively increased.
  • the weight range of the rare earth element may be 0.03 to 2.0% by weight. Specifically, it may be 0.1 to 2.0% by weight. More specifically, it may be 0.1 to 0.9% by weight.
  • Zinc like aluminum, serves to increase the strength of the alloy through solid solution strengthening and precipitation strengthening.
  • the upper limit of zinc may be limited as in one embodiment of the present invention.
  • Zn may include less than 5% by weight. More specifically, it may be 4.5% by weight or less. More specifically, it may be 0.1 to 4.5% by weight.
  • the upper limit of calcium may be limited as in one embodiment of the present invention.
  • Ca may be included in an amount of 2.0% by weight or less with respect to 100% by weight of the entire magnesium alloy material. More specifically, it may range from 0.5 to 2.0% by weight.
  • a magnesium alloy material having excellent corrosion resistance can be provided.
  • Yttrium like calcium, serves to increase the ignition temperature of magnesium alloys.
  • the effect of improving ignition resistance may be insignificant due to low ignition temperature.
  • the content of yttrium is too large, the fraction of yttrium-containing particles may be excessive, which may cause problems of promoting microgalvanic corrosion and an increase in alloy material price.
  • a method of manufacturing a magnesium alloy material based on 100 wt% of the magnesium alloy material, Al: 0.03 to 16.0 wt%, Mn: 0.015 to 1.0 wt%, Sc: 0.02 to 0.5 wt%, rare earth elements (RE): preparing a molten metal containing 0.03 to 2.0% by weight, residual Mg and unavoidable impurities; And casting the molten metal to produce a cast material. It may provide a method for manufacturing a magnesium alloy material comprising a.
  • the rare earth element may include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or a combination thereof.
  • the molten metal may further include Zn: less than 5.0% by weight based on 100% by weight.
  • Zn: may further include 0.1 to 4.5% by weight.
  • the molten metal may further include Ca: 2.0% by weight or less based on 100% by weight. Specifically, Ca: 0.5 to 2.0% by weight may be further included.
  • the molten metal may further include Y: 0.5% by weight or less with respect to 100% by weight. Specifically, Y: may further include 0.3% by weight or less.
  • the reason for limiting the composition and composition of the molten metal is the same as the reason for limiting the composition and composition of the magnesium alloy material described above, and thus will be omitted.
  • Casting the molten metal to produce a cast material may be carried out in a temperature range of 600 °C to 800 °C.
  • sand casting gravity casting, pressure casting, low pressure casting, dewaxing casting, thin plate casting, strip casting, single roll casting, continuous casting, electromagnetic casting, electromagnetic continuous casting, die casting, precision casting, freezing casting, spray casting, centrifugal Casting, reaction high casting, quench casting, lateral extrusion casting, single belt casting, twin belt casting, shell mold casting, cast-free casting, 3D printing, or a combination of these can be produced.
  • it is not limited to this.
  • a processing process consisting of rolling, extrusion, drawing, forging, or a combination of the cast material may be further included.
  • the cast material manufactured above can be further subjected to a subsequent processing process.
  • the cast material may be provided in the form of a rolled material, an extruded material, a drawn material, a forged material, or a product.
  • the processing process including rolling, extrusion, drawing, forging, or a combination thereof is not specifically limited, and any method can be performed after appropriate heat treatment if necessary using a cast material.
  • a magnesium cast material including the components and compositions disclosed in Tables 1 to 6 and a magnesium rolled material comprising the components and compositions disclosed in Table 7 below were prepared.
  • Mg (99.9%), Net Al (99.9%), Net Mn (99.9%), Net Sc (99.9%), Net RE (99.9%), Net Zn (99.9%), Net Ca (99.9%), Net Y (99.9%) was used.
  • the Mg alloys were dissolved in a graphite crucible using a high-frequency induction melting furnace so as to have the compositions shown in Tables 1 to 7 below.
  • a mixture of SF 6 and CO 2 was applied to the top of the molten metal to block contact with the atmosphere.
  • the molten metal is maintained at 750° C. for 10 minutes, and then the molten metal is poured into a steel mold preheated to 200° C. at a molten metal temperature determined in the range of 650 to 750° C. depending on the alloy composition, and thus 80 mm high, 40 mm wide and 12 mm thick
  • the size of the cast material was prepared.
  • the surface was processed to a thickness of 8.5 mm.
  • the temperature of the specimen was maintained at 350°C over each rolling pass, and until the final specimen thickness of 1 mm was reached at a rolling reduction rate of 20% per pass using a constant speed rolling mill with a rolling roll temperature set at 200°C.
  • the rolling process was performed.
  • the annealing treatment was performed at 345° C. for 1 hour on the produced rolled material.
  • the magnesium alloy material was immersed in a 3.5 wt% NaCl solution equal to NaCl concentration in seawater. At this time, the immersion test was performed at 25°C (room temperature).
  • the magnesium alloy material was immersed in a 3.5% by weight NaCl solution at room temperature for 72 hours, and a surface oxide layer formed upon immersion was removed using a chromic acid (CrO 3 ) solution having a concentration of 200 g/L.
  • CrO 3 chromic acid
  • composition ranges of aluminum, manganese, and scandium are the same as in the examples, but when the rare earth element is not added, it can be confirmed that the corrosion rate is faster than when the rare earth element is added.
  • the results for the alloying material further including Y can be seen. It has been found that even in alloys containing Y for improving the ignition resistance, the improved corrosion resistance is maintained due to the use of Sc and RE elements, and the corrosion resistance is slightly improved. However, when the content of yttrium is excessive, the fraction of particles containing yttrium is excessive, which promotes microgalvanic corrosion and may result in an alloy price, thereby limiting the Y addition amount to 0.3% by weight or less.
  • Table 7 below is an evaluation result of the rolled material of the magnesium alloy prepared as a component of Examples and Comparative Examples.
  • FIG. 1 is a scanning electron microscope photograph showing secondary phase particles formed inside a rolled Mg-3Al-0.3Mn-0.1Sc-1Zn alloy. Through this microstructure analysis, it can be seen that Al-Mn-Fe-based particles and Al-Mn-Sc particles including impurities Fe are formed inside the rolled material.
  • FIG. 2 is a scanning electron microscope photograph showing secondary phase particles formed inside a rolled Mg-3Al-0.3Mn-0.1Sc-1Zn-0.3Gd alloy.
  • a rare earth element such as Gd
  • the core containing impurities Fe is located in the center and the Al-Mn-RE particles are located in the core- It can be seen that a double particle in the form of a core (shell) was formed.
  • particles containing Fe are known to activate microgalvanic corrosion in magnesium alloys due to their high electrochemical potential. As described above, hydrogen reduction reaction cannot occur in a corrosive environment in particles existing in the core of double particles. These particles fail to activate microgalvanic corrosion, which can improve the corrosion resistance of the alloy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Forging (AREA)
  • Heat Treatment Of Steel (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

La présente invention concerne un matériau d'alliage de magnésium et son procédé de production. Un matériau d'alliage de magnésium, dans un mode de réalisation de la présente invention, comprend : par rapport à 100 % en poids du matériau d'alliage de magnésium, 0,03 % à 16,0 % en poids d'Al ; 0,015 % à 1,0 % en poids de Mn ; 0,02 % à 0,5 % en poids de Sc, 0,03 % à 2,0 % en poids d'un élément de terre rare (RE) ; Mg résiduel; et des impuretés inévitables, l'élément des terres rares (RE) pouvant comprendre La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, ou des combinaisons de ceux-ci.
PCT/KR2019/016489 2018-12-14 2019-11-27 Matériau d'alliage de magnésium et son procédé de production Ceased WO2020122472A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201980065305.1A CN112789360A (zh) 2018-12-14 2019-11-27 镁合金材料及其制造方法
DE112019006206.9T DE112019006206T5 (de) 2018-12-14 2019-11-27 Magnesiumlegierungsmaterial und sein Herstellungsverfahren
JP2021529823A JP7323616B2 (ja) 2018-12-14 2019-11-27 マグネシウム合金材およびその製造方法
US17/132,613 US20210115538A1 (en) 2018-12-14 2020-12-23 Magnesium alloy

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KR1020180161659A KR102210236B1 (ko) 2018-12-14 2018-12-14 마그네슘 합금재 및 이의 제조방법
KR10-2018-0161659 2018-12-14

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US17/132,613 Continuation-In-Part US20210115538A1 (en) 2018-12-14 2020-12-23 Magnesium alloy

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WO2020122472A2 true WO2020122472A2 (fr) 2020-06-18
WO2020122472A3 WO2020122472A3 (fr) 2020-10-01

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CN (1) CN112789360A (fr)
DE (1) DE112019006206T5 (fr)
WO (1) WO2020122472A2 (fr)

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CN112746210A (zh) * 2021-02-01 2021-05-04 太原理工大学 一种多元微合金化镁合金及其制法和板材挤压成形工艺
CN116770140A (zh) * 2023-04-28 2023-09-19 中国地质大学（武汉） 镁合金涂层材料、钢制饰品表面涂层及其制备方法与应用

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CN112410632A (zh) * 2020-11-20 2021-02-26 中国科学院长春应用化学研究所 一种Mg-Gd-Y-Nd高强韧稀土镁合金及其制备方法
CN112410632B (zh) * 2020-11-20 2022-03-08 中国科学院长春应用化学研究所 一种Mg-Gd-Y-Nd高强韧稀土镁合金及其制备方法
CN112746210A (zh) * 2021-02-01 2021-05-04 太原理工大学 一种多元微合金化镁合金及其制法和板材挤压成形工艺
CN116770140A (zh) * 2023-04-28 2023-09-19 中国地质大学（武汉） 镁合金涂层材料、钢制饰品表面涂层及其制备方法与应用

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DE112019006206T5 (de) 2021-09-30
WO2020122472A3 (fr) 2020-10-01
JP2022513645A (ja) 2022-02-09
CN112789360A (zh) 2021-05-11
US20210115538A1 (en) 2021-04-22
KR20200073472A (ko) 2020-06-24

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